LIQUID – LIQUID EXTRACTION

INTRODUCTION

Liquid–liquid extraction (LLE), also known as solvent extraction and partitioning, is a method to

separate compounds or metal complexes, based on their relative solubilities in two different immiscible
liquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer of one or more
species from one liquid into another liquid phase, generally from aqueous to organic. The transfer is
driven by chemical potential, i.e. once the transfer is complete, the overall system of protons and
electrons that make up the solutes and the solvents are in a more stable configuration (lower free energy).
The solvent that is enriched in solute(s) is called extract. The feed solution that is depleted in solute(s) is
called the raffinate. LLE is a basic technique in chemical laboratories, where it is performed using a
variety of apparatus, from separatory funnels to countercurrent distribution equipment called as mixer
settlers. This type of process is commonly performed after a chemical reaction as part of the work-up,
often including an acidic work-up.

The term partitioning is commonly used to refer to the underlying chemical and physical processes
involved in liquid–liquid extraction, but on another reading may be fully synonymous with it. The
term solvent extraction can also refer to the separation of a substance from a mixture by preferentially
dissolving that substance in a suitable solvent. In that case, a soluble compound is separated from an
insoluble compound or a complex matrix.

From a hydrometallurgical perspective, solvent extraction is exclusively used in separation and

purification of uranium and plutonium, zirconium and hafnium, separation of cobalt and nickel,
separation and purification of rare earth elements etc., its greatest advantage being its ability to
selectively separate out even very similar metals. One obtains high-purity single metal streams on
'stripping' out the metal value from the 'loaded' organic wherein one can precipitate or deposit the metal
value. Stripping is the opposite of extraction: Transfer of mass from organic to aqueous phase.

LLE is also widely used in the production of fine organic compounds, the processing of perfumes, the
production of vegetable oils and biodiesel, and other industries. It is among the most common initial
separation techniques, though some difficulties result in extracting out closely related functional groups.
Liquid–liquid extraction is possible in non-aqueous systems: In a system consisting of a molten metal in
contact with molten salts, metals can be extracted from one phase to the other. This is related to
a mercury electrode where a metal can be reduced, the metal will often then dissolve in the mercury to
form an amalgam that modifies its electrochemistry greatly.

For example, it is possible for sodium cations to be reduced at a mercury cathode to form sodium

amalgam, while at an inert electrode (such as platinum) the sodium cations are not reduced. Instead,
water is reduced to hydrogen. A detergent orfine solid can be used to stabilize an emulsion, or third phase
.
 Figure - Counter Current Extraction Unit

History

Solvent extraction is an old practice done for years. It is the main process in perfume development and it
is also used to obtain dyes from various sources.

Modern use has made this process an essential practice in scientific laboratories. In 1872 Berthelot and
Jungfleisch introduced the concept of the partition coefficient. Followed by an introduction in phase
equilibrium by Gibbs. Many of these advances occurred as the chemical industry grew as well.

Further research and improvements to the process affected the commercial applications. Due to the
advantages of solvent extraction various chemical treatment methods for refining coal tar products and
mineral oil were replaced.
MEASURES OF EFFECTIVENESS

Distribution ratio

In solvent extraction, a distribution ratio is often quoted as a measure of how well-extracted a species is.
The distribution ratio (Kd) is equal to the concentration of a solute in the organic phase divided by its
concentration in the aqueous phase. Depending on the system, the distribution ratio can be a function of
temperature, the concentration of chemical species in the system, and a large number of other
parameters. Note that D is related to the ΔG of the extraction process.

Sometimes, the distribution ratio is referred to as the partition coefficient, which is often expressed as
the logarithm. Note that a distribution ratio for uranium and neptunium between two inorganic solids
(zirconolite and perovskite) has been reported. In solvent extraction, two immiscible liquids are shaken
together. The more polar solutes dissolve preferentially in the more polar solvent, and the less polar
solutes in the less polar solvent. In this experiment, the nonpolar halogens preferentially dissolve in the
non-polar mineral oil.

Although the distribution ratio and partition coefficient are often used synonymously, they are not
necessarily so. Solutes may exist in more than one form in any particular phase, which would mean that
the partition coefficient (Kd) and distribution ratio (D) will have different values. This is an important
distinction to make as whilst the partition coefficient has a fixed value for the partitioning of a solute
between two phases, the distribution ratio changes with differing conditions in the solvent.

After performing liquid–liquid extraction, a quantitative measure must be taken to determine the ratio of
the solution’s total concentration in each phase of the extraction. This quantitative measure is known as
the distribution ratio or distribution coefficient.

Separation factors

The separation factor is one distribution ratio divided by another; it is a measure of the ability of the
system to separate two solutes. For instance, if the distribution ratio for nickel(DNi) is 10 and the
distribution ratio for silver (DAg) is 100, then the silver/nickel separation factor (SF Ag/Ni) is equal to
DAg/DNi = SFAg/Ni = 10.
Decontamination factor

This is used to express the ability of a process to remove a contaminant from a product. For instance, if a
process is fed with a mixture of 1:9 cadmium to indium, and the product is a 1:99 mixture of cadmium
and indium, then the decontamination factor (for the removal of cadmium) of the process is 0.11 / 0.01 =
11.

Slopes of graphs

The easy way to work out the extraction mechanism is to draw graphs and measure the slopes. If for an
extraction system the D value is proportional to the square of the concentration of a reagent (Z) then the
slope of the graph of log10(D) against log10([[Z]]) will be two.

Measures of success

Success of liquid–liquid extraction is measured through separation factors and decontamination factors.
The best way to understand the success of an extraction column is through the liquid–liquid equilibrium
(LLE) data set. The data set can then be converted into a curve to determine the steady state partitioning
behavior of the solute between the two phases. The y-axis is the concentration of solute in the extract
(solvent) phase, and the x-axis is the concentration of the solute in the raffinate phase. From here, one can
determine steps for optimization of the process.

TECHNIQUES

Batchwise single stage extractions

This is commonly used on the small scale in chemical labs. It is normal to use a separating funnel.
Processes include DLLME and direct organic extraction.
Dispersive liquid–liquid microextraction (DLLME)

A process used to extract small amounts of organic compounds from water samples. This process is done
by injecting small amounts of an appropriate extraction solvent (C 2Cl4) and a disperser solvent (acetone)
into the aqueous solution. The resulting solution is then centrifuged to separate the organic and aqueous
layers. This process is useful in extraction organic compounds such as organochloride and
organophsophorus pesticides, as well as substituted benzene compounds from water samples.

Direct organic extraction

By mixing partially organic soluble samples in organic solvent (toluene, benzene, xylene), the organic
soluble compounds will dissolve into the solvent and can be separated using a separatory funnel. This
process is valuable in the extraction of proteins and specifically phosphoprotein and phosphopeptide
phosphatases.

Another example of this application is extracting anisole from a mixture of water and 5% acetic

acid using ether, then the anisole will enter the organic phase. The two phases would then be separated.
The acetic acid can then be scrubbed (removed) from the organic phase by shaking the organic extract
with sodium bicarbonate. The acetic acid reacts with the sodium bicarbonate to form sodium
acetate, carbon dioxide, and water.

Caffeine can also be extracted from coffee beans and tea leaves using a direct organic extraction. The
beans or leaves can be soaked in ethyl acetate which favorably dissolves the caffeine, leaving a majority of
the coffee or tea flavor remaining in the initial sample.

Multistage countercurrent continuous processes

Coflore continuous countercurrent extractor.

These are commonly used in industry for the processing of metals such as the lanthanides; because the
separation factors between the lanthanides are so small many extraction stages are needed. In the
multistage processes, the aqueous raffinate from one extraction unit is fed to the next unit as the aqueous
feed, while the organic phase is moved in the opposite direction. Hence, in this way, even if the separation
between two metals in each stage is small, the overall system can have a higher decontamination factor.
Multistage countercurrent arrays have been used for the separation of lanthanides. For the design of a
good process, the distribution ratio should be not too high (>100) or too low (<0.1) in the extraction
portion of the process. It is often the case that the process will have a section for scrubbing unwanted
metals from the organic phase, and finally a stripping section to obtain the metal back from the organic
phase.

Mixer–settlers

Battery of mixer-settlers counter currently interconnected. Each mixer-settler unit provides a single stage
of extraction. A mixer settler consists of a first stage that mixes the phases together followed by a
quiescent settling stage that allows the phases to separate by gravity.
In the multistage countercurrent process, multiple mixer settlers are installed with mixing and settling
chambers located at alternating ends for each stage (since the outlet of the settling sections feed the inlets
of the adjacent stage’s mixing sections). Mixer-settlers are used when a process requires longer residence
times and when the solutions are easily separated by gravity. They require a large facility footprint, but
do not require much headspace, and need limited remote maintenance capability for occasional
replacement of mixing motors. (Colven, 1956; Davidson, 1957)

4 stage battery of mixer-settlers for counter-current extraction.

Centrifugal extractors

Centrifugal extractors mix and separate in one unit. Two liquids will be intensively mixed between the
spinning rotor and the stationary housing at speeds up to 6000 RPM. This develops great surfaces for an
ideal mass transfer from the aqueous phase into the organic phase. At 200–2000 g, both phases will be
separated again. Centrifugal extractors minimize the solvent in the process, optimize the product load in
the solvent and extract the aqueous phase completely. Counter current and cross current extractions are
easily established.
 Figure – Centrifugal Extractors

Extraction without chemical change

Some solutes such as noble gases can be extracted from one phase to another without the need for a
chemical reaction (see absorption). This is the simplest type of solvent extraction. When a solvent is
extracted, two immiscible liquids are shaken together. The more polar solutes dissolve preferentially in
the more polar solvent, and the less polar solutes in the less polar solvent. Some solutes that do not at first
sight appear to undergo a reaction during the extraction process do not have distribution ratio that is
independent of concentration. A classic example is the extraction of carboxylic acids (HA) into nonpolar
media such as benzene. Here, it is often the case that the carboxylic acid will form a dimer in the organic
layer so the distribution ratio will change as a function of the acid concentration (measured in either
phase).
For this case, the extraction constant k is described by k = [[HAorganic]]2/[[HAaqueous].

Solvation mechanism

Using solvent extraction it is possible to extract uranium, plutonium, thorium and many rare earth

elements from acid solutions in a selective way by using the right choice of organic extracting solvent and
diluent. One solvent used for this purpose is the organophosphate tributyl phosphate (TBP).
The PUREX process that is commonly used in nuclear reprocessing uses a mixture of tri-n-butyl
phosphate and an inert hydrocarbon (kerosene), the uranium(VI) are extracted from strong nitric
acid and are back-extracted (stripped) using weak nitric acid. An organic soluble
uranium complex [UO2(TBP)2(NO3)2] is formed, then the organic layer bearing the uranium is brought
into contact with a dilute nitric acid solution; the equilibrium is shifted away from the organic soluble
uranium complex and towards the free TBP and uranyl nitrate in dilute nitric acid. The plutonium(IV)
forms a similar complex to the uranium(VI), but it is possible to strip the plutonium in more than one
way; a reducing agent that converts the plutonium to the trivalent oxidation state can be added. This
oxidation state does not form a stable complex with TBP and nitrate unless the nitrate concentration is
very high (circa 10 mol/L nitrate is required in the aqueous phase). Another method is to simply use
dilute nitric acid as a stripping agent for the plutonium. This PUREX chemistry is a classic example of
a solvation extraction.
Here in this case DU = k TBP2[[NO3]]2

Ion exchange mechanism

Another extraction mechanism is known as the ion exchange mechanism. Here, when an ion is

transferred from the aqueous phase to the organic phase, another ion is transferred in the other direction
to maintain the charge balance. This additional ion is often a hydrogen ion; for ion exchange
mechanisms, the distribution ratio is often a function of pH. An example of an ion exchange extraction
would be the extraction of americium by a combination of terpyridine and a carboxylic acid in tert-
butyl benzene. In this case
DAm = k terpyridine1carboxylic acid3H+−3
Another example is the extraction of zinc, cadmium, or lead by a dialkyl phosphinic acid (R2PO2H) into a
nonpolar diluent such as an alkane. A non-polar diluent favours the formation of uncharged non-
polar metal complexes.

Some extraction systems are able to extract metals by both the solvation and ion exchange mechanisms;
an example of such a system is the americium (and lanthanide) extraction from nitric acid by a
combination of 6,6'-bis-(5,6-dipentyl-1,2,4-triazin-3-yl)-2,2'-bipyridine and 2-bromohexanoic acid in tert-
butyl benzene. At both high- and low-nitric acid concentrations, the metal distribution ratio is higher
than it is for an intermediate nitric acid concentration.

Ion pair extraction

It is possible by careful choice of counterion to extract a metal. For instance, if the nitrate concentration

is high, it is possible to extract americium as an anionic nitrate complex if the mixture contains
a lipophilic quaternary ammonium salt.

An example that is more likely to be encountered by the 'average' chemist is the use of a phase transfer
catalyst. This is a charged species that transfers another ion to the organic phase. The ion reacts and then
forms another ion, which is then transferred back to the aqueous phase.

For instance, the 31.1 kJ mol−1 is required to transfer an acetate anion into nitrobenzene, while the
energy required to transfer a chloride anion from an aqueous phase to nitrobenzene is 43.8 kJ
mol−1. Hence, if the aqueous phase in a reaction is a solution of sodium acetate while the organic phase is
a nitrobenzene solution of benzyl chloride, then, when a phase transfer catalyst, the acetate anions can be
transferred from the aqueous layer where they react with the benzyl chloride to form benzyl acetate and
a chloride anion. The chloride anion is then transferred to the aqueous phase. The transfer energies of
the anions contribute to that given out by the reaction.

A 43.8 to 31.1 kJ mol−1 = 12.7 kJ mol−1 of additional energy is given out by the reaction when compared
with energy if the reaction had been done in nitrobenzene using one equivalent weight of
a tetraalkylammonium acetate.
Types of aqueous two-phase extractions

Polymer–polymer systems. In a Polymer–polymer system, both phases are generated by a dissolved

polymer. The heavy phase will generally be a polysaccharide, and the light phase is
generally Polyethylene glycol (PEG). Traditionally, the polysaccharide used is dextran. However, dextran
is relatively expensive, and research has been exploring using less expensive polysaccharides to generate
the heavy phase. If the target compound being separated is a protein or enzyme, it is possible to
incorporate a ligand to the target into one of the polymer phases. This improves the target's affinity to
that phase, and improves its ability to partition from one phase into the other. This, as well as the absence
of solvents or other denaturing agents, makes polymer–polymer extractions an attractive option for
purifying proteins. The two phases of a polymer–polymer system often have very similar densities, and
very low surface tension between them. Because of this, demixing a polymer–polymer system is often
much more difficult than demixing a solvent extraction. Methods to improve the demixing
include centrifugation, and application of an electric field. Polymer–salt systems. Aqueous two-phase
systems can also be generated by generating the heavy phase with a concentrated salt solution. The
polymer phase used is generally still PEG. Generally, a kosmotropic salt, such as Na3PO4 is used, however
PEG–NaCl systems have been documented when the salt concentration is high enough. Since polymer–
salt systems demix readily they are easier to use. However, at high salt concentrations, proteins generally
either denature, or precipitate from solution. Thus, polymer–salt systems are not as useful for purifying
proteins.

Ionic liquids systems. Ionic liquids are ionic compounds with low melting points. While they are not
technically aqueous, recent research has experimented with using them in an extraction that does not use
organic solvents.

APPLICATIONS

 DNA purification: The ability to purify DNA from a sample is important for many modern
biotechnology processes. However, samples often contain nucleases that degrade the target DNA
before it can be purified. It has been shown that DNA fragments will partition into the light phase of
a polymer–salt separation system. If ligands known to bind and deactivate nucleases are incorporated
into the polymer phase, the nucleases will then partition into the heavy phase and be deactivated.
Thus, this polymer–salt system is a useful tool for purifying DNA from a sample while simultaneously
protecting it from nucleases.
 Food industry: The PEG–NaCl system has been shown to be effective at partitioning small
molecules, such as peptides and nucleic acids. These compounds are often flavorants or odorants. The
system could then be used by the food industry to isolate or eliminate particular
flavors. Caffeine extraction used to be done using liquid–liquid extraction, specifically direct and
indirect liquid–liquid extraction (Swiss Water Method), but has since moved towards super-critical
CO2 as it is cheaper and can be done on a commercial scale .
 Analytical chemistry: Often there are chemical species present or necessary at one stage of
sample processing that will interfere with the analysis. For example, some air monitoring is
performed by drawing air through a small glass tube filled with sorbent particles that have been
coated with a chemical to stabilize or derivatize the analyte of interest. The coating may be of such a
concentration or characteristics that it would damage the instrumentation or interfere with the
analysis. If the sample can be extracted from the sorbent using a nonpolar solvent (such as toluene or
carbon disulfide), and the coating is polar (such as HBr or phosphoric acid) the dissolved coating will
partition into the aqueous phase. Clearly the reverse is true as well, using polar extraction solvent and
a nonpolar solvent to partition a nonpolar interferent. A small aliquot of the organic phase (or in
the latter case, polar phase) can then be injected into the instrument for analysis.

 Purification of amines: Amines (analogously to ammonia) have a lone pair of electrons on the

nitrogen atom that can form a relatively weak bond to a hydrogen atom. It is therefore the case that
under acidic conditions amines are typically protonated, carrying a positive charge and under basic
conditions they are typically deprotonated and neutral. Amines of sufficiently low molecular weight
are rather polar and can form hydrogen bonds with water and therefore will readily dissolve in
aqueous solutions. Deprotonated amines on the other hand, are neutral and have greasy, nonpolar
organic substituents, and therefore have a higher affinity for nonpolar inorganic solvents. As such
purification steps can be carried out where an aqueous solution of an amine is neutralized with a base
such as sodium hydroxide, then shaken in a separatory funnel with a nonpolar solvent that is
immiscible with water. The organic phase is then drained off. Subsequent processing can recover the
amine by techniques such as recrystallization, evaporation or distillation; subsequent extraction back
to a polar phase can be performed by adding HCl and shaking again in a separatory funnel (at which
point the ammonium ion could be recovered by adding an insoluble counterion), or in either phase,
reactions could be performed as part of a chemical synthesis.

Equipment

While solvent extraction is often done on a small scale by synthetic lab chemists using a separatory
funnel, Craig apparatus or membrane-based techniques,  it is normally done on the industrial scale using
machines that bring the two liquid phases into contact with each other. Such machines
include centrifugal contactors, Thin Layer Extraction, spray columns, pulsed columns, and mixer-
settlers.
Extraction of metals

The extraction methods for a range of metals include

 Cobalt – The extraction of cobalt from hydrochloric acid using alamine 336 (tri-octyl/decyl amine)

in meta-xylene. Cobalt can be extracted also using Cyanex 272 {bis-(2,4,4-trimethylpentyl) phosphinic
acid0}

 Copper – Copper can be extracted using hydroxyoximes as extractants, a recent paper describes
an extractant that has a good selectivity for copper over cobalt and nickel.

 Neodymium – This rare earth is extracted by di(2-ethyl-hexyl)phosphoric acid into hexane by an

ion exchange mechanism.

 Nickel – Nickel can be extracted using di(2-ethyl-hexyl)phosphoric acid and tributyl phosphate in

a hydrocarbon diluent (Shellsol).

 Palladium and platinum – Dialkyl sulfides, tributyl phosphate and alkyl amines have been used
for extracting these metals.

 Polonium is produced in reactors from natural 209Bi, bombarded with neutrons, creating 210Bi,

which then decays to 210Po via beta-minus decay. The final purification is done pyrochemically
followed by liquid-liquid extraction vs. sodium hydroxide at 500 deg C.
  Zinc and cadmium – The zinc and cadmium are both extracted by an ion exchange process,
the N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) acts as a masking agent for the
zinc and an extractant for the cadmium. In the modified Zincex process, zinc is separated from
most divalent ions by solvent extraction. D2EHPA (Di (2) ethyl hexyl phosphoric acid) is used for
this. A zinc ion replaces the proton from two D2EHPA molecules. To strip the zinc from the
D2EHPA, sulfuric acid is used, at a concentration of above 170g/l (typically 240-265g/l).

CONCLUSION

Liquid–liquid extraction, also known as partitioning, is a separation process consisting of the transfer of
a solute from one solvent to another, the two solvents being immiscible or partially miscible with each
other. Frequently, one of the solvents is water or an aqueous mixture and the other is a non-polar organic
liquid. As in all extraction processes, liquid–liquid extraction comprises a step of mixing (contacting)
followed by a step of phase separation. It is important to consider both steps in the selection of solvents
and modes of operation. Thus, while vigorous mixing is favorable to the transfer of the extractable from
one solvent to the other, it may also impair the ease of phase separation by forming emulsions.
 MINI PROJECT
On
Liquid – Liquid Extraction
Submitted as a part of the theoretical paper
INDUSTRIAL STOICHIOMETRY (CHE - 302) of B.Tech course

of session 2017 – 2021

Supervised By Mrs. Sutapa Roy and Dr Asit K. Saha

By
NAME UNIVERSITY ROLL SIGNATURE
No.
DIPRO DAS 10300617051
DIPANJAN DAS 10300617052
DHIMAN SAHOO 10300617053
BIPASHA BARAI 10300617054
ARU SHARKA SINGHA 10300617055
ARKADIP DAS 10300617056
ARGHYADEEP DAS 10300617058
ANKITA KUMARI 10300617060
ANKITA KESHRI 10300617061

Department of Chemical Engineering

 Haldia Institute of Technology, Haldia

Date of Submission:- 30/11/2018

CONTENTS

 INTRODUCTION

 HISTORY

 MEASURES OF EFFECTIVENESS

 TECHNIQUES

 APPLICATIONS

 EQUIPMENTS

 EXTRACTION OF METALS

 CONCLUSION
REFERENCES

1. Stoichiometry and process calculation By K.V. NARAYANAN and B. LAXMIKUTTY

2. https://en.wikipedia.org/wiki/Liquid%E2%80%93liquid_extraction

3. https://www.aiche.org/resources/publications/cep/2015/november/design-principles-
liquid-liquid-extraction